SU997797A1 - Catalyst for oxidation of acetaldehide - Google Patents

Description

The invention relates to the field of catalysts for the acetaldegnd process of the phase-phase oxidation of acetaldehyde to simultaneously produce acetic acid and acetic anhydrogen (Drida).

Catalysts for the joint production of acetic acid and acetic anhydride by liquid phase oxidation of acetaldehyde are known, which are organic salts of various metals, such as manganese, cobalt, copper acetates, stearates and cobalt oleates, and copper.

Closest to the present invention is a catalyst for the oxidation of acetaldehyde, consisting of copper and co-sieve acetates in a ratio of 1: (1.1-1, 5) C.2.

The disadvantage of the known catalyst is the low yield of acetic anhydride, amounting to 55-60 mol%.

The purpose of the invention is to increase the selectivity of the catalyst.

This goal is achieved by the fact that the catalyst for the oxidation of acetaldehyde, including copper acetate and cobalt acetate, additionally contains bromopentaminobaltidibromide or cobalt trisacetylacetonate

with the following content of components, g / l.

Copper Acetate 3.0-3.98 Cobalt Acetate 0.22-2.33 BroLpentaminokobaltidibro0, 01-0.015 mid

or cobalt tris acetylaceto10

0.17-2.11 nat

The catalyst is prepared by dissolving in hydrous acetic acid hydrated copper salts and cobalt: copper acetate (C2 (i, ace tate cobalt Co (C2 and trivalent complex compound; cobalt.

In the data catalyst, the ratio between the concentration of copper acetate

20 and the total content of divalent and trivalent cobalt compounds is 71: 1.

In the presence of the attached catalyst, the oxidation of acetaldehyde is pro (25 proceeds with the selectivity of the formation of acetic anhydride 64-75 mol.%.

Example 1. 0.398 g of Cu (C2H3O2) 2-20 copper acetate, 0.233 g of Co (C2H362) 4 HjO cobalt acetate, 30 g of bromopentaamine cobaltidibromo With (NHg) BrJBr immediately before the experiment is dissolved in 16.7 ml of glacial acetic acid . Then, 83.3 ml of acetic anhydride was added to the resulting solution, 70 ml of the resulting mixture was poured into the reactor.

The resulting catalyst contains copper acetate 3.98 g / l, cobalt acetate 2.33 g / l, Co (MH3) 5 Vg Vg 0.015 g / l. The ratio between the concentration of copper acetate and the total content of Co (I I) and Co (IIt) is 1.71: 1.

The activity of this catalyst is determined in the reaction of the acetic aldehyde oxidative oxidation in a lab bubbling type apparatus with a glass reactor. The catalyst solution is maintained in a reactor in a suspended state on a perforated plate by the pressure of a nitrogen-air mixture. The feed rate1 of nitrogen is 90.5 l / hr of air 180.8 l / h, - acetaldehyde 200-240 ml / h.

The selectivity of the formation of acetic anhydride in the presence of this catalyst is 60.6 mol%.

Example 2. About, 398 g of copper acetate, 0.233 g of cobalt acetate and 0.001 romompentaaminocobaltidibromide are dissolved according to the procedure described in example 1.

The catalyst thus prepared contains, g / l: copper acetate 3.98, cobalt acetate 2.33; (NH-j) 5 0.01.

According to the procedure described in Example 1, the liquid-phase oxidation of acetaldehyde is carried out in the presence of the proposed catalyst, the selectivity of the formation of acetic anhydride is 69.2%. EXAMPLE 3 According to the procedure described in Example 1, a catalyst was prepared containing, g / l; copper acetate 3.98; cobalt acetate 1.94 and cobalt trisacetylacetonate — Co (Cj-H-jOj) 0.39.

The selectivity of the formation of acetic anhydride during the liquid-phase oxidation of acetaldehyde in the presence of this catalyst is 69.8 mol%.

Example4. According to the procedure described in Example 1, a catalyst is prepared containing, g / L copper acetate 3.98; cobalt acetate 1.7b and Co (C5H702) i 0.58.

The selectivity of the formation of acetic anhydride in the reaction of the phase-phase oxidation of acetaldehyde in the presence of a catalyst is 75.2 mol%.

EXAMPLE 5 According to the procedure described in Example 1 B, a catalyst containing, g / l, is prepared: copper acetate 3.98, cobalt acetate 0.58 and cobalt trisacetylacetonate 1.75.

Selectivity of the formation of acetic anhydride in the liquid phase oxide

The scientific research institute of acetaldehyde in the presence of this catalyst is 70.5 mol.%.

Example According to the procedure described in Example 1, a catalyst is prepared containing, g / l: copper acetate 3.98; cobalt acetate 0,22 and cobalt trisacetylacetonate 2,11.

The selectivity of the formation of acetic anhydride in the reaction of liquid-phase oxidation of acetaldehyde in the presence of this catalyst is 67.0 mol%.

Example7. According to the procedure described in Example 1, a catalyst is prepared containing: g / l: copper acetate 3.0; cobalt acetate 0.83 and cobalt trisacetylacetonate 0.17.

In the presence of this catalyst ce; Acetic anhydride formation, with liquid-phase acetaldehyde oxidation of 73.6 mol%.

Example8. According to the procedure described in Example 1, a catalyst was prepared having the following composition, g / l: copper acetate 3.45, cobalt acetate 0.87; cobalt trisacetylacetonate 0.28. .

The selectivity of the formation of acetic anhydride during the liquid-phase oxidation of acetaldehyde in the presence of the proposed catalyst is 73.9 mol.

PRI me R 9 (for comparison). . According to the procedure described in Example 1, a catalyst was prepared having a composition, g / l copper acetate 3.98, cobalt acetate 2.33.

The selectivity of acetic anhydride in the liquid phase oxidation of acetaldehyde in the presence of this catalyst is 59.0 mol%.

Example 10 (for comparison) According to the procedure described in Example 1, a catalyst is prepared having the following composition, g / l :. copper acetate one 3.0; cobalt afjeTaT 1.0.

The selectivity of the formation of acetic anhydride in the process of liquid-phase oxidation of acetaldehyde in the presence of this catalyst is 61.0 mol.%.

Example 11 (for comparison). According to the procedure described in Example 1, a catalyst was prepared having a composition, g / l: copper acetate 3.45, cobalt acetate 1.15.

The selectivity of the formation of acetic anhydride during the liquid-phase oxidation of acetaldehyde in the presence of this catalyst is 61.0 wt.%.

The table shows the results of testing the proposed and well-known catalysts in the reaction of liquid-phase acetaldehyde oxidation.

From the results shown in the table, it follows that the proposed catalyst (1-8} leads to a significant increase in the selectivity of the catalyst in the direction of formation of acetic anhydride up to 67-75.2% against 59.0-61.0% in the presence of known catalysts (9-11).

tat cobalt, o tl and h and hell and u | s with the fact that, with a higher catalyst selectivity, it additionally contains brs mpyontaminokobaltidibrsmyd or cobalttryysatytylatatatatat next content of anyone

Copper Acetate 3.0-3.98 Cobalt Acetate 0.22-2.33

Ie OCHNIKI information taken into account in the examination

1.Denisov E.T. and others. Mechanism. liquid-phase oxidation of oxygen-containing compounds., Minsk, Science and Technology, 1975, p. 139.

2.Patent of France No. 1252746,. cl. C 07 C, publ. 1962 (prototype).

Claims (1)

Claim The catalyst for the oxidation of acetaldehyde, including copper acetate and cobalt acetate, is 35 s in that, in order to increase the selectivity of the catalyst, it additionally contains bromopenta aminocobaltidibromide or cobaltric acetylacetate at the following content of ingredients, g / l: Copper Acetate 3.0-3.98 Cobalt Acetate 0.22-2.33 Brompentaaminocobalt idibromide 0.01-0.015 or cobalttrisacetylacetonate 0.17-2.11